Efficient synthesis of porous triazine-based macrocycles with 22-carbon and 6-nitrogen ring atoms and their adsorption/desorption of non-volatile organic compounds.

Porous triazine-based macrocycles with 22-carbon and 6-nitrogen ring atoms were efficiently synthesized and used for adsorbing bisphenol A, sulfamethoxazole, sodium dodecyl sulfate, and polyoxyethylene laural ether from aqueous media; after adsorption, simple extraction to desorb the guests from these porous macrocycles demonstrates a facile and efficient approach for porous materials to adsorb and desorb non-volatile organic compounds, thus being potentially applied to other surfactants or antibiotics.

Coordination Chemistry and Reactivity of a Lewis Acidic Di-Zinc Framework Supported by Bisphenoxymethanone Ligands.

We present the synthesis, structural characterization, and reactivity studies of a tetra-zinc complex supported by the bisphenoxymethanone ligands and its transformation into various di-zinc architectures. Our findings highlight the potential of these complexes in molecular recognition, supramolecular chemistry, and catalysis.

Cobalt(II) Single-Ion Magnet Coordinated by Double Deprotonation of 2,2'-Bipyridine-6,6'-diol Ligands.

In this study, we synthesized a new Co(II) complex, [NMe][Co(bpyO)] (), using deprotonated 2,2'-bipyridine-6,6'-diol ligands (bpyO ). This compound exhibits a significant zero-field splitting () value. The far-infrared magneto spectroscopy and high-frequency and field electron paramagnetic resonance (HFEPR) measurements indicated that compound possesses = -54.

A Bis-Cyclopentadienyl Ligand-Supported Di-Iron Trihydride Motif as a Synthon for Access to Heterobimetallic Trinuclear Complexes.

Herein, we report the synthesis of a flexible bis-cyclopentadienyl ligand (the doubly deprotonated form of (1,3-bis(2,4-di--butylcyclopentadienyldimethylsilyl)benzene)), demonstrating its ability to stabilize a series of di-iron hydrido complexes. Notably, this ligand facilitates the isolation of an unprecedented anionic cyclopentadienyl ligand-supported di-iron trihydride complex, (), functioning as a synthon for the [Fe(μ-H)] core and providing access to heterobimetallic complexes - with coinage metals.

Rhodium(I)/Chiral Diene Complexes Catalyzed Asymmetric Desymmetrization of Alkynyl-Tethered 2,5-Cyclohexadienones Through an Arylative Cyclization Cascade.

-hydrobenzofurans, -hydroindoles, and -hydrindanes, privileged structural motifs found in numerous biologically active natural and synthetic compounds, are efficiently prepared by a Rh(I)-catalyzed cascade -arylation/1,4-addition protocol. This approach starts with the regioselective -arylation of the alkyne tethered to 2,5-hexadienone moieties, using a chiral Rh(I) catalyst generated from a chiral bicyclo[2.2.

Isolable Tin(II) Hydrides Featuring Sterically Undemanding Pincer-Type Ligands and Their Dehydrogenative Sn-Sn Bond Forming Reactions to Distannynes Promoted by Lewis Acidic Tri--butylborane.

Unlike isolable tin(II) hydrides supported by bulky ligands reported in the literature, this research describes the synthesis and characterization of thermally stable tin(II) hydrides () and () stabilized by sterically undemanding N,N,N-coordinating pincer-type ligands ( = 2,5-dipyridyl-3,4-diphenylpyrrolato; = 2,5-bis(6-methylpyridyl)pyrrolato). The results from previous reports reveal that attempts to access tin(II) hydrides containing less-bulky ligands have had limited success, and decomposition to tin(I) distannynes often occurs. The key to the successful isolation of and is the identification of the role of Lewis acidic BBu, generated upon delivering hydride from commonly used hydride reagents M[BBuH] ("selectrides", M = Li or K).

Enantioselective Synthesis of 1-Aryl Tetrahydroisoquinolines by the Rhodium-Catalyzed Reaction of 3,4-Dihydroisoquinolinium Tetraarylborates.

The 1-aryl tetrahydroisoquinolines (1-aryl THIQs) are omnipresent in biologically active molecules. Here we report on the direct asymmetric synthesis of these valuable compounds via the reaction of 3,4-dihydroisoquinolinium tetraarylborates. The dual roles of anionic tetraarylborates, which function as both prenucleophiles and stabilizers of 3,4-dihydroisoquinolinium cations, enable this rhodium(I)-catalyzed protocol to convergently provide enantioenriched 1-aryl THIQs in good yields (≤95%) with ≤97% ee, as demonstrated by the formal synthesis of (-)-solifenacin and the facile synthesis of (-)-Cryptostyline I.

Photoinduced Mechanical Motions of Pseudorotaxane Crystals Composed of Azobenzene and Ferrocenyl Groups on an Axle and a Crown Ether Ring.

This work describes the design and characterization of photoresponsive dynamic pseudorotaxane crystals composed of azobenzene and ferrocenyl groups in an ammonium cation axle component threaded through dibenzo[24]crown-8 ether rings. Pseudorotaxanes provide flexibility for cis and trans isomerization of azobenzene groups in a crystal state, enabling reversible bending motions under alternating 360 and 445 nm laser irradiation. For such bending motions, strained azobenzene structures were essential; these motifs were obtained by increasing the bulkiness of the substituents on the axle and ring molecules.

Enantioselective Rhodium-Catalyzed Allylation of Aliphatic Imines: Synthesis of Chiral C-Aliphatic Homoallylic Amines.

Reported herein is a method for the efficient syntheses of optically active 1-alkyl homoallylic amines in yields up to 95%, 13.5:1 dr, and 98% ee under mild, aqueous reaction conditions, via the Rh-catalyzed asymmetric allylation of aliphatic aldimines. This method provides a streamlined synthetic platform for the preparation of indolizidine and piperidine alkaloids, thus demonstrating its usefulness.

Asymmetric Synthesis of Functionalized Phenylalanine Derivatives via Rh-Catalyzed Conjugate Addition and Enantioselective Protonation Cascade.

The asymmetric conjugate addition of arylboronic acids to -phthalimidodehydroalanine catalyzed by Rh(I)/ enables the facile preparation of chiral functionalized phenylalanines. The reaction proceeds by a conjugate addition and enantioselective protonation cascade, affording a rhodium enolate that undergoes -face protonation. The reaction tolerates various arylboronic acids and can be used in the gram-scale synthesis of ()-phenylalanine hydrochloride, demonstrating the reaction scope and the synthetic feasibility of the process.

Mononuclear Manganese(III) Superoxo Complexes: Synthesis, Characterization, and Reactivity.

Metal-superoxo species are typically proposed as key intermediates in the catalytic cycle of dioxygen activation by metalloenzymes involving different transition metal cofactors. In this regard, while a series of Fe-, Co-, and Ni-superoxo complexes have been reported to date, well-defined Mn-superoxo complexes remain rather rare. Herein, we report two mononuclear Mn-superoxo species, Mn(BDPP)(O) (, HBDPP = 2,6-bis((2-()-diphenylhydroxylmethyl-1-pyrrolidinyl)methyl)pyridine) and Mn(BDPP)(O) (, HBDPP = 2,6-bis((2-()-di(4-bromo)phenylhydroxyl-methyl-1-pyrrolidinyl)methyl)pyridine), synthesized by bubbling O into solutions of their Mn precursors, Mn(BDPP) () and Mn(BDPP) (), at -80 °C.

Asymmetric Synthesis of β-Aryl β-Imido Sulfones Using Rhodium Catalysts with Chiral Diene Ligands: Synthesis of Apremilast.

A chiral rhodium(I)-diene catalyst enabled the one-step synthesis of β-aryl β-imido sulfones under mild reaction conditions. By selection of the chiral diene ligand L1a or L2, each enantiomer of the chiral β-aryl β-imido sulfone target can be accessed with high stereoselectivity. Demonstration of the scope of the reaction, which includes the synthesis of an N-protected chiral β-amino β-phenyl sulfone, culminated with the efficient synthesis of the heteroatom-rich active pharmaceutical ingredient apremilast.

Directed Self-Assembly of C-Symmetric, Oxidovanadate-Centered, Vanadyl(V) Quadruplexes for Ba- and Hg-Specific Recognition, Transport, and Recovery.

Directed assembly of loosely, Na-bound, oxidovanadate-centered quartets of C-symmetry from tailor-made chiral N-salicylidene-vanadyl(V) complexes, for the first time, allows for highly efficient Ba- or Hg-specific detection (by V NMR and VCD), transport (forming a unique helical capsule or a capped square planar complex, respectively), and green recovery from an aqueous phase containing 4 different alkaline earth ions or from at least 10 different metal ions of similar size and charge capacity into the CHCl layer without interference from oxa- or oxophilic ions like Mg, Ca, Cu, Cd, and Pb.

Access to β-Amino Acids via Enantioselective 1,4-Arylation of β-Nitroacrylates Catalyzed by Chiral Rhodium Catalysts.

The highly enantioselective conjugate addition of a variety of arylboronic acids to β-nitroacrylates is reported to provide optically active α-aryl β-nitropropionates in up to 70% yields and >99.5% ee's, which are useful building blocks for preparing chiral β-amino acids. The applicability of this transformation is demonstrated by converting 3aa into the β-amino acid 5 and transforming 3ap to β-amino ester 7 via reduction and reductive N-alkylation.

Ligand-Unsupported Cuprophilicity in the Preparation of Dodecacopper(I) Complexes and Raman Studies.

Synthesis and characterization of two dodecacopper(I) extended metal atom chains (EMAC) assembled by two hexadentate bis(pyridylamido)amidinate-supported hexacopper(I) string complexes (monomers) via the ligand-unsupported cuprophilicity are described. In addition to short unsupported Cu-Cu contacts, two hexacopper fragments in these two dodecacopper EMACs show a bent conformation based on X-ray crystallography. Compared with their THF-bound hexacopper(I) monomers and protonated ligands, these ligand-unsupported cuprophilic interactions are shown to be weak by Raman spectroscopy.

Reversible Laser-Induced Bending of Pseudorotaxane Crystals.

This study investigated the dynamic photoresponse of pseudorotaxane crystals with azobenzene and ferrocenyl groups in the axle component. X-ray crystallography showed pseudorotaxanes with a methylazobenzene group and a dibromophenylene ring in the cyclic component to exhibit twisting of the trans-azobenzene groups at torsion angles of 17° and 38°, respectively. Repeated alternating laser irradiation of the crystals at 360 and 445 nm produced bending of 20-30° in opposite directions, with no evidence of decay.

Rh-Catalyzed Enantioselective Allylation of N-Tosyl- and N-Nosylaldimines: Total Synthesis of (-)-Crispine A.

The unprecedented development of asymmetric Rh-catalyzed 1,2-allylation of N-Ts- and N-Ns-aldimines is achieved. This protocol utilizes potassium allyltrifluoroborates and various aldimines to generate enantioenriched homoallylic amines in the presence of 3.0 mol % of Rh(I)/L1b catalyst with up to 90% yield, 98% ee (R = H), and 10:1 diastereoselectivity (R = Me or Ph), yielding the same major diastereomer when using potassium (E)- and (Z)-crotyltrifluoroborate.

Molecular Re Cages: Structural and Luminescent Properties.

Versatile building block [{Re(CO) } (C N S )] (1 a; C N S =cyanurate trianion) reacts with linear dipyridyl ligands [i.e., pyrazine (pz), 4,4'-bipyridine (bpy), 1,2-bis(4-pyridyl)ethylene (bpe), bis(4-pyridyl)acetylene (bpa), and 1,4-bis(pyridyl-4-ylethynyl)benzene (bpb)] and a tripyridyl ligand [1,3,5-tris(4-pyridylethynyl)benzene (tpb)] to afford a series of molecular cages [{Re(CO) } (L) (C N S ) ] [L=pz (2), bpy (3), bpe (4), bpa (5), bpb (6)] and [{Re(CO) } (tpb) (C N S ) ] (7) under solvothermal conditions.

Synthesis and Characterization of an Eclipsed Digermylene as a Building Block to Construct a Cyclic Octagermylene.

The preparation of an unprecedented Ge -Ge bonded digermylene [K {Ge (μ-κ :η :η -2,6-(2,6- Pr C H -N) -4-CH C H N) }] in an eclipsed conformation stabilized by two bridging diamidopyridyl ligands is presented. Although it exhibits an eclipsed conformation, the Ge-Ge bond length is 2.5168(6) Å, which is shorter than those in the trans-bent and gauche digermylenes.

Design and Synthesis of Chiral Diene Ligands for Rh -Catalyzed Enantioselective Arylation of N-DPP-protected Aldimines: Synthesis of the Antifungal Agent Bifonazole.

Herein we describe the design and synthesis of a novel family of bifunctional, chiral bicyclo[2.2.1]heptadiene ligands bearing aryl and secondary amido groups, and demonstrate their usefulness in the Rh -catalyzed enantioselective addition reaction of arylboronic acids to N-diphenylphosphinyl (N-DPP)-protected aldimines.

A Structurally Characterized Nonheme Cobalt-Hydroperoxo Complex Derived from Its Superoxo Intermediate via Hydrogen Atom Abstraction.

Bubbling O into a THF solution of Co(BDPP) (1) at -90 °C generates an O adduct, Co(BDPP)(O) (3). The resonance Raman and EPR investigations reveal that 3 contains a low spin cobalt(III) ion bound to a superoxo ligand. Significantly, at -90 °C, 3 can react with 2,2,6,6-tetramethyl-1-hydroxypiperidine (TEMPOH) to form a structurally characterized cobalt(III)-hydroperoxo complex, Co(BDPP)(OOH) (4) and TEMPO.

Synthesis of Quaternary-Carbon-Containing β -Amino Acids by the Rh -Catalyzed Enantioselective Arylation of α-Substituted β-Nitroacrylates.

An enantioselective Rh -catalyzed conjugate addition reaction of α-substituted β-nitroacrylates with various arylboronic acids by using chiral Rh diene catalysts is described for the first time. The addition reaction proceeds under mild conditions in a range of common organic solvents and additives, and it affords the corresponding quaternary-carbon-containing α,α-disubstituted β-nitropropionate products in up to 63 % yield and 99 % ee. Reaction of either (E)- or (Z)-β-nitroacrylates provided the same enantiomer of the product, and a range of esters and aryl groups were tolerated.

A Family of Multiply Bonded Dimolybdenum Boraamidinates with the Formal Mo-Mo Bond Orders of 3, 4, 4.5, and 5.

A boraamidinato ligand [PhB(N-2,6-(i) Pr2 C6 H3 )2 ](2-) was employed to stabilize a new family of multiply bonded dimolybdenum complexes [MoCl(μ-κ(2) -PhB(N-2,6-(i) Pr2 C6 H3 )2 )]2 (4) and [Mo(μ-κ(2) -PhB(N-2,6-(i) Pr2 C6 H3 )2 )]2 (n-) (n=0 (5), 1 (6), 2 (7)), with the respective formal Mo-Mo bond orders of 3, 4, 4.5, and 5. Each metal center in 5-7 is two-coordinate with respect to the ligands.

[Ni(OMe)]-mediated reductive activation of CO affording a Ni(κ-OCO) complex.

Carbon dioxide is expected to be employed as an inexpensive and potential feedstock of C sources for the mass production of valuable chemicals and fuel. Versatile chemical transformations of CO, insertion of CO producing bicarbonate/acetate/formate, cleavage of CO yielding μ-CO/μ-oxo transition-metal complexes, and electrocatalytic reduction of CO affording CO/HCOOH/CHOH/CH/CH/oxalate were well documented. Herein, we report a novel pathway for the reductive activation of CO by the [Ni(OMe)(P(CH-3-SiMe-2-S))] complex, yielding the [Ni(κ-OCO˙)(P(CH-3-SiMe-2-S))] complex.

Encapsulation of Formaldehyde and Hydrogen Cyanide in an Open-Cage Fullerene.

Reaction of C63 NO2 (Ph)2 (Py) (1) with o-phenylenediamine and pyridine produces a mixture of C63 H4 NO2 (Ph)2 (Py)(N2 C6 H4 ) (2) and H2 O@2. Compound 2 is a new open-cage fullerene containing a 20-membered heterocyclic orifice, which has been fully characterized by NMR spectroscopy, high-resolution mass spectrometry, and X-ray crystallography. The elliptical orifice of 2 spans 7.